技术领域technical field
本发明涉及一种阻燃树脂组合物。The invention relates to a flame retardant resin composition.
背景技术Background technique
目前，常用的电线电缆包覆材料以及电器、充电器的插头为聚氯乙烯(PVC)与乙烯-乙酸乙烯共聚物(EVA)材料。由于环保的要求越来越高，制作电线电缆包覆以及电器、充电器的插头的材料要求满足ROHS(《关于限制在电子电器设备中使用某些有害成分的指令》(Restriction of HazardousSubstances))环保检测，而且不能含有卤素。而PVC材料中含有大量的卤素原子，在燃烧时会释放出有毒气体，从而对环境产生破坏并毒害人体健康。另外，EVA材料的耐热温度以及耐油耐腐蚀性能较差。At present, commonly used wire and cable covering materials and plugs of electrical appliances and chargers are polyvinyl chloride (PVC) and ethylene-vinyl acetate copolymer (EVA) materials. Due to the increasing requirements for environmental protection, the materials for making wire and cable coverings and plugs for electrical appliances and chargers are required to meet ROHS ("Restriction of Hazardous Substances" (Restriction of Hazardous Substances)) environmental protection detection, and must not contain halogens. The PVC material contains a large number of halogen atoms, which will release toxic gases when burned, which will damage the environment and poison human health. In addition, the EVA material has poor heat resistance temperature and oil resistance and corrosion resistance.
因此，需要寻求具有较高的热变型温度以及耐油耐腐蚀性能很好，并且在燃烧时无毒无害的电线、电缆包覆材料，用来替代目前的PVC与EVA线材包覆材料。Therefore, it is necessary to seek wire and cable covering materials with high heat distortion temperature, good oil resistance and corrosion resistance, and non-toxic and harmless when burning, to replace the current PVC and EVA wire covering materials.
热塑性弹性体材料既具有硫化橡胶的物理机械性能又具有热塑性塑料的工艺加工性能，可谓是塑料和橡胶优点的优势组合。近十余年来，电子电器、通讯与汽车行业的快速发展带动了热塑性弹性体市场的高速发展。由于不需经过热硫化，使用通用的塑料加工设备即可完成产品生产。随着人们环保意识的增强，对高分子材料在生产以及使用过程中是否环保与安全也越来越被人们所重视。而以氢化苯乙烯-丁二烯嵌段共聚物(SEBS)为基础的热塑性弹性体由于SEBS中弹性体嵌段已完全氢化，因此SEBS具有优良的耐老化性并能在高温下进行加工，而且对臭氧、紫外线、电弧具有良好的耐受性，还具有良好的耐油、耐化学品腐蚀性以及优异的耐低温性。Thermoplastic elastomer materials have both the physical and mechanical properties of vulcanized rubber and the processing properties of thermoplastics, which can be described as an advantageous combination of the advantages of plastics and rubber. In the past ten years, the rapid development of electronic appliances, communications and automobile industries has driven the rapid development of the thermoplastic elastomer market. Since there is no need for heat vulcanization, the product can be produced using general-purpose plastic processing equipment. With the enhancement of people's awareness of environmental protection, people pay more and more attention to whether the polymer materials are environmentally friendly and safe in the process of production and use. The thermoplastic elastomer based on hydrogenated styrene-butadiene block copolymer (SEBS) has excellent aging resistance and can be processed at high temperature because the elastomer block in SEBS has been completely hydrogenated, and It has good resistance to ozone, ultraviolet rays, electric arc, good oil resistance, chemical corrosion resistance and excellent low temperature resistance.
CN1884367A中公开了一种膨胀型低烟无卤热塑性阻燃橡胶，由下述重量百分比的组分配制而成：SEBS，15-60％；软化油，1-25％；抗氧剂0.2-0.5％；纳米无机物，3-7.5％；氮-磷复合阻燃剂，32-46％；聚丙烯，1-30％；分散剂，0.1-0.5％。该阻燃橡胶还含有聚乙烯，所述聚乙烯占重量百分比的1-5％；该阻燃橡胶还含有硅树脂，该硅树脂为热固性塑料，所述硅树脂占重量百分比的1-3％；所述软化油为石蜡基油、环烷油中的一种；所述分散剂为硬脂酸盐、低分子酰胺中的一种。CN1884367A discloses an intumescent low-smoke halogen-free thermoplastic flame-retardant rubber, which is prepared from the following components in weight percent: SEBS, 15-60%; softening oil, 1-25%; antioxidant 0.2-0.5% %; nano-inorganic matter, 3-7.5%; nitrogen-phosphorus composite flame retardant, 32-46%; polypropylene, 1-30%; dispersant, 0.1-0.5%. The flame-retardant rubber also contains polyethylene, and the polyethylene accounts for 1-5% by weight; the flame-retardant rubber also contains silicone resin, which is a thermosetting plastic, and the silicone resin accounts for 1-3% by weight The softening oil is one of paraffin base oil and naphthenic oil; the dispersant is one of stearate and low molecular weight amides.
CN1772807A公开了一种高阻燃高耐温低烟无卤电缆护套料，其主要原料是SEBS、白油、PP、PS、马来酸酐接枝的SEBS、阻燃剂、偶联剂、超微细白烟、硅氧烷、抗氧剂、环保色粉；电缆护套料主要由如下比例的成分组成：100份SEBS、20-100份白油、0-100份PP、0-20份PS、5份马来酸酐接枝的SEBS、150-350份阻燃剂、3-6份偶联剂、3-5份超微细白烟、4份硅氧烷、2份抗氧剂、2-10份环保色粉。其中，阻燃剂是磷氮系阻燃剂。硅氧烷主要是起到润滑的作用。CN1772807A discloses a high flame-retardant, high-temperature-resistant, low-smoke, halogen-free cable sheathing material, whose main raw materials are SEBS, white oil, PP, PS, SEBS grafted with maleic anhydride, flame retardant, coupling agent, super Fine white smoke, siloxane, antioxidant, environmentally friendly toner; cable sheath material is mainly composed of the following components: 100 parts of SEBS, 20-100 parts of white oil, 0-100 parts of PP, 0-20 parts of PS , 5 parts of SEBS grafted with maleic anhydride, 150-350 parts of flame retardant, 3-6 parts of coupling agent, 3-5 parts of ultrafine white smoke, 4 parts of siloxane, 2 parts of antioxidant, 2- 10 parts eco-friendly toner. Among them, the flame retardant is a phosphorus nitrogen flame retardant. Siloxane mainly acts as a lubricant.
上述专利中所使用的白油是指白色矿物油，通常是使用石蜡基矿物油的馏份油经过脱蜡或者是使用环烷基馏份油来制取。在上述两个专利中所使用的软化油或白油虽然可以使该护套料的硬度降低，但使该护套料的力学性能较差，尤其是使100％定伸强度较低，并增加了阻燃剂的用量。另外，CN1772807A中采用通用的磷氮系阻燃剂，在树脂的加工过程中该阻燃剂与基体树脂SEBS的结合力不好，添加量也比较大，阻燃剂与基体树脂在双螺杆挤出过程中会阻燃剂会发生部分分解，引起物料的膨胀，从而使该护套料的力学性能和阻燃性能下降。The white oil used in the above-mentioned patents refers to white mineral oil, which is usually produced by dewaxing or using naphthenic distillate oils from distillate oils of paraffin-based mineral oils. Although the softening oil or white oil used in the above two patents can reduce the hardness of the sheath material, it makes the mechanical properties of the sheath material poor, especially makes the 100% modulus lower and increases The amount of flame retardant used. In addition, CN1772807A adopts a general-purpose phosphorus-nitrogen flame retardant. During the processing of the resin, the bonding force between the flame retardant and the base resin SEBS is not good, and the addition amount is relatively large. The flame retardant and the base resin are extruded in a twin-screw The flame retardant will be partially decomposed during the extraction process, which will cause the expansion of the material, thereby reducing the mechanical properties and flame retardancy of the sheath material.
发明内容Contents of the invention
本发明的目的在于克服上述现有技术中电缆护套料的力学性能较差，尤其是100％定伸强度较低的缺陷，提供一种力学性能较好，尤其是100％定伸强度较高的阻燃树脂组合物。The purpose of the present invention is to overcome the poor mechanical properties of cable sheathing materials in the prior art, especially the defects of low 100% elongation strength, and provide a kind of better mechanical properties, especially higher 100% elongation strength. flame retardant resin composition.
本发明提供了一种阻燃树脂组合物，该组合物含有氢化苯乙烯-丁二烯嵌段共聚物、聚丙烯和/或聚苯乙烯、阻燃剂和相容剂，其中，所述组合物还含有硅油。The invention provides a flame retardant resin composition, which contains hydrogenated styrene-butadiene block copolymer, polypropylene and/or polystyrene, flame retardant and compatibilizer, wherein the combination It also contains silicone oil.
根据本发明提供的组合物，由于组合物中含有硅油，可以对氢化苯乙烯-丁二烯嵌段共聚物(SEBS)进行充油以降低硬度，由于硅油以硅氧(Si-O)键为主链，因而不会影响SEBS的拉伸强度，而且可以辅助阻燃剂在组合树脂的表面形成致密的炭层，从而提高树脂组合物的氧指数，降低火焰的传播速度。因而，本发明提供的阻燃树脂组合物的力学性能较好，而且100％定伸强度较高。According to the composition provided by the present invention, since the composition contains silicone oil, the hydrogenated styrene-butadiene block copolymer (SEBS) can be oil-extended to reduce the hardness, because the silicone oil is based on the silicon oxygen (Si-O) bond. Main chain, so it will not affect the tensile strength of SEBS, and can assist the flame retardant to form a dense charcoal layer on the surface of the combined resin, thereby increasing the oxygen index of the resin composition and reducing the flame propagation speed. Therefore, the flame-retardant resin composition provided by the invention has better mechanical properties and higher 100% modulus.
具体实施方式Detailed ways
本发明提供的阻燃树脂组合物含有氢化苯乙烯-丁二烯嵌段共聚物、聚丙烯和/或聚苯乙烯、阻燃剂和相容剂，其中，所述组合物还含有硅油。The flame retardant resin composition provided by the invention contains hydrogenated styrene-butadiene block copolymer, polypropylene and/or polystyrene, a flame retardant and a compatibilizer, wherein the composition also contains silicone oil.
根据本发明提供的组合物，在优选情况下，基于100重量份的氢化苯乙烯-丁二烯嵌段共聚物，所述硅油的含量为20-60重量份，所述聚丙烯和/或聚苯乙烯的含量为15-40重量份，所述阻燃剂的含量为20-50重量份，所述相容剂的含量为5-10重量份。According to the composition provided by the present invention, preferably, based on 100 parts by weight of the hydrogenated styrene-butadiene block copolymer, the content of the silicone oil is 20-60 parts by weight, and the polypropylene and/or polypropylene The content of styrene is 15-40 parts by weight, the content of the flame retardant is 20-50 parts by weight, and the content of the compatibilizer is 5-10 parts by weight.
根据本发明提供的组合物，采用硅油可以对氢化苯乙烯-丁二烯嵌段共聚物(SEBS)进行充油以降低组合物的硬度，由于硅油以硅氧(Si-O)键为主链，因而不会影响SEBS的拉伸强度，而且可以辅助阻燃剂在组合树脂的表面形成致密的炭层，从而提高树脂组合物的氧指数，降低火焰的传播速度。优选所述硅油的20-50mPa.s，密度为0.945-0.965g.cm-3。According to the composition provided by the present invention, the hydrogenated styrene-butadiene block copolymer (SEBS) can be oil-extended to reduce the hardness of the composition by using silicone oil, because the silicone oil has a silicon oxygen (Si-O) bond as the main chain , so it will not affect the tensile strength of SEBS, and can assist the flame retardant to form a dense charcoal layer on the surface of the combined resin, thereby increasing the oxygen index of the resin composition and reducing the flame propagation speed. Preferably, the silicone oil has a density of 20-50 mPa.s and a density of 0.945-0.965 g.cm-3 .
根据本发明提供的组合物，所述硅油优选可以选用甲基硅油、二甲基硅油、乙基硅油、苯基硅油、甲基苯基硅油、甲基乙氧基硅油、甲基乙烯基硅油、甲基羟基硅油和含氰硅油中的一种或几种。可以选用的商购的硅油为德国瓦克、道康宁以及深圳市吉鹏硅氟材料公司的硅油。According to the composition provided by the present invention, the silicone oil can preferably be selected from methyl silicone oil, dimethyl silicone oil, ethyl silicone oil, phenyl silicone oil, methylphenyl silicone oil, methyl ethoxy silicone oil, methyl vinyl silicone oil, One or more of methyl hydroxy silicone oil and cyanosilicone oil. The commercially available silicone oils that can be used are the silicone oils from Wacker, Dow Corning, and Shenzhen Jipeng Silicon Fluorine Materials Co., Ltd.
根据本发明提供的组合物，所述阻燃剂可以选用各种阻燃剂。然而，本发明优选所述阻燃剂为含有磷酸酯、聚磷酸胺和包覆红磷的复合阻燃剂，所述磷酸酯优选为双酚A双(二苯基磷酸酯)、间苯二酚(二苯基磷酸酯)和磷酸三苯酯中的一种或几种；所述聚磷酸胺的聚合度为1500以上；所述包覆红磷的含磷量为45-75重量％，所述包覆红磷可选用本领域公知的各种包覆红磷，本发明优选白度化包覆红磷，例如连云港信托硅化的FRW30。According to the composition provided by the present invention, the flame retardant can be selected from various flame retardants. However, the present invention prefers that the flame retardant is a composite flame retardant containing phosphoric acid ester, polyphosphate amine and coated red phosphorus, and the phosphoric acid ester is preferably bisphenol A bis(diphenyl phosphate), resorcinol One or more of phenol (diphenyl phosphate) and triphenyl phosphate; the degree of polymerization of the polyphosphate amine is more than 1500; the phosphorus content of the coated red phosphorus is 45-75% by weight, The coated red phosphorus can be selected from various coated red phosphorus known in the art, and the whitening coated red phosphorus is preferred in the present invention, such as FRW30 of Lianyungang Trust Silicification.
本发明所选用的复合阻燃剂，其中，磷酸酯在常温下为液体或者具有非常低的熔点，可以润湿包覆的白度化红磷以及膨胀型阻燃剂。而且，膨胀型阻燃剂与包覆的白度化红磷、磷酸酯复配可在本发明的树脂组合物表面形成炭性发泡成多孔的炭层，从而提高阻燃剂的阻燃效率，减少阻燃剂的用量。本发明所选用的复合阻燃剂在高温时可以在基体树脂氢化苯乙烯-丁二烯嵌段共聚物(SEBS)的表面形成酯交联，抑止挥发性与低分子量裂解产物的生成，增大了芳香族炭化层的生成速度并减少了烟和有毒气体的释放。同时，由于本发明所选用的复合阻燃剂通过相容剂与主体树脂SEBS达到了非常好的相容性，因此可以提高本发明的阻燃树脂组合物的力学性能。In the composite flame retardant selected by the present invention, the phosphoric acid ester is liquid at normal temperature or has a very low melting point, and can wet the coated whiteness red phosphorus and the intumescent flame retardant. Moreover, the compounding of the intumescent flame retardant with coated white phosphorus and phosphoric acid ester can form a charcoal foaming porous carbon layer on the surface of the resin composition of the present invention, thereby improving the flame retardant efficiency of the flame retardant , reduce the amount of flame retardants. The composite flame retardant selected by the present invention can form ester crosslinking on the surface of matrix resin hydrogenated styrene-butadiene block copolymer (SEBS) at high temperature, suppress the generation of volatile and low molecular weight cracking products, increase This increases the rate of formation of the aromatic char layer and reduces the release of smoke and toxic gases. At the same time, since the composite flame retardant selected in the present invention achieves very good compatibility with the main resin SEBS through the compatibilizer, the mechanical properties of the flame retardant resin composition of the present invention can be improved.
根据本发明提供的组合物，在优选情况下，在所述阻燃剂中，磷酸酯、聚磷酸胺和包覆红磷的重量比为1∶0.1-2∶1-5。According to the composition provided by the present invention, preferably, in the flame retardant, the weight ratio of phosphoric acid ester, polyphosphate amine and coated red phosphorus is 1:0.1-2:1-5.
根据本发明提供的组合物，在优选情况下，所述氢化苯乙烯-丁二烯嵌段共聚物(SEBS)在25℃下的甲苯溶液粘度为1200-2000MPa.s，采用以三氯甲烷为溶剂的溴碘法测量的氢化度为97.2-100％，且苯乙烯单元与丁二烯单元的质量比为1∶1-4。满足上述条件的可以选用的商购的代表性的SEBS可以为巴陵石化YH-561、台橡3151和科腾1652。According to the composition provided by the present invention, in preferred cases, the toluene solution viscosity of the hydrogenated styrene-butadiene block copolymer (SEBS) at 25°C is 1200-2000MPa.s, using chloroform as The hydrogenation degree of the solvent measured by the bromine iodine method is 97.2-100%, and the mass ratio of styrene units to butadiene units is 1:1-4. Commercially available representative SEBS that meet the above conditions can be Baling Petrochemical YH-561, TSRC 3151 and Kraton 1652.
本文所使用的术语“氢化”是指对树脂中不饱和键进行加氢；术语“氢化度”指树脂的加氢指数。The term "hydrogenation" used herein refers to the hydrogenation of unsaturated bonds in the resin; the term "degree of hydrogenation" refers to the hydrogenation index of the resin.
根据本发明提供的组合物，在优选情况下，所述聚丙烯的熔融指数在230℃、2.16kg砝码的测量条件下为5-15g/10min，拉伸强度为15-25MPa，可选用广州石化的聚丙烯CJS700，燕山石化的聚丙烯K1008，燕山石化工具类聚丙烯k9026和K8303。According to the composition provided by the present invention, preferably, the melt index of the polypropylene is 5-15g/10min under the measurement conditions of 230°C and 2.16kg weight, and the tensile strength is 15-25MPa. Petrochemical polypropylene CJS700, Yanshan Petrochemical polypropylene K1008, Yanshan Petrochemical tool polypropylene k9026 and K8303.
所述聚苯乙烯在23℃时的抗冲击强度为9-13kJ/m2，且熔融指数在230℃、5kg砝码的测量条件下为5-10g/10min，可以选用的商购的聚苯乙烯为奇美公司PH-88和杨子巴斯夫476L。The impact strength of the polystyrene at 23°C is 9-13kJ/m2 , and the melt index is 5-10g/10min under the measurement conditions of 230°C and 5kg weight. The commercially available polystyrene The ethylene is Chimei PH-88 and Yangzi BASF 476L.
根据本发明提供的组合物，所述相容剂可以选用本领域技术人员公知的各种相容剂，本发明优选采用乙烯-丙烯酸甲酯共聚物和/或乙烯-丙烯酸酯-马来酸酐三元共聚物，此相容剂可与SEBS树脂之间形成化学键架桥结构，从而使SEBS树脂极化，增加SEBS树脂与阻燃剂的结合力，提高本发明的树脂组合物的拉伸强度、断裂伸长率等。According to the composition provided by the present invention, the compatibilizer can be selected from various compatibilizers known to those skilled in the art, and the present invention preferably adopts ethylene-methyl acrylate copolymer and/or ethylene-acrylate-maleic anhydride Metapolymer, this compatibilizer can form chemical bond bridging structure between SEBS resin, thereby SEBS resin is polarized, increases the binding force of SEBS resin and flame retardant, improves the tensile strength, elongation at break, etc.
根据本发明提供的组合物，在优选情况下，所述乙烯-丙烯酸甲酯共聚物的熔融指数在190℃、2.16kg砝码的测量条件下为5-20g/10min，其中，乙烯单元与丙烯酸甲酯单元的质量比为1∶0.1-0.5；所述乙烯-丙烯酸酯-马来酸酐三元共聚物的熔融指数在190℃、2.16kg砝码的测量条件下为9-15g/10min，乙烯单元与丙烯酸酯单元和马来酸酐单元的质量比为1∶0.1-0.3∶0.05-0.1，并且所述丙烯酸酯为丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯和甲基丙烯酸异丁酯中的一种或几种。可以选用的商购的乙烯-丙烯酸甲酯共聚物为埃克森美孚的TC120、TC115；可以选用的商购的乙烯-丙烯酸酯-马来酸酐三元共聚物为阿科玛LOTADER 4210。According to the composition provided by the present invention, preferably, the melt index of the ethylene-methyl acrylate copolymer is 5-20g/10min under the measurement conditions of 190°C and a weight of 2.16kg, wherein the ethylene unit and acrylic acid The mass ratio of the methyl ester unit is 1:0.1-0.5; the melt index of the ethylene-acrylic acid ester-maleic anhydride terpolymer is 9-15g/10min under the measurement conditions of 190°C and a weight of 2.16kg, and the ethylene The mass ratio of unit to acrylate unit and maleic anhydride unit is 1:0.1-0.3:0.05-0.1, and the acrylate is methyl acrylate, ethyl acrylate, butyl acrylate and isobutyl methacrylate one or several. Available commercially available ethylene-methyl acrylate copolymers are ExxonMobil's TC120 and TC115; available commercially available ethylene-acrylate-maleic anhydride terpolymers are Arkema LOTADER 4210.
根据本发明提供的组合物，在优选情况下，所述组合物还含有加工助剂，基于100重量份的氢化苯乙烯-丁二烯嵌段共聚物，所述加工助剂的含量为3-10重量份。According to the composition provided by the present invention, under preferred circumstances, the composition also contains a processing aid, based on 100 parts by weight of hydrogenated styrene-butadiene block copolymer, the content of the processing aid is 3- 10 parts by weight.
根据本发明提供的组合物，所述加工助剂为本领域技术人员公知的各种加工助剂，例如可选用抗氧剂、防滴落剂、除酸剂和润滑剂中的一种或几种，并且，基于100重量份的氢化苯乙烯-丁二烯嵌段共聚物，所述抗氧剂的含量为0.3-3重量份，所述防滴落剂的含量为1-5重量份，所述除酸剂的含量为0.3-1重量份，所述润滑剂的含量为0.3-3重量份。According to the composition provided by the present invention, the processing aid is various processing aids known to those skilled in the art, for example, one or more of antioxidants, anti-dripping agents, acid scavenger and lubricants can be selected. species, and, based on 100 parts by weight of hydrogenated styrene-butadiene block copolymer, the content of the antioxidant is 0.3-3 parts by weight, and the content of the anti-dripping agent is 1-5 parts by weight, The content of the acid scavenger is 0.3-1 parts by weight, and the content of the lubricant is 0.3-3 parts by weight.
所述防滴落剂优选为聚四氟乙烯(PTFE)。The anti-dripping agent is preferably polytetrafluoroethylene (PTFE).
所述除酸剂优选为硬脂酸钙，该硬脂酸钙可以起到除酸的作用，并对树脂颜色的稳定以及树脂的防腐蚀等具有直接的贡献，另外硬脂酸钙可提高最终产品在挤出成型压制成型时的可加工性。Described acid removal agent is preferably calcium stearate, and this calcium stearate can play the effect of acid removal, and has direct contribution to the stability of resin color and the anticorrosion of resin etc., and calcium stearate can improve final The processability of the product during extrusion molding and compression molding.
所述润滑剂可以选用本领域技术人员公知的各种润滑剂，例如为乙撑双硬酯酰胺、接枝乙撑双硬酯酰胺、硅酮和金属皂盐中的一种或几种。本发明优选采用硅酮，硅酮不仅可以使本发明的树脂组合物在挤塑程中降低熔融压力、熔体粘度、降低内应力并可以明显增加树脂组合物的氧指数含量，而且可以大大提高树脂组合物的表面光洁度。The lubricant can be selected from various lubricants known to those skilled in the art, for example, one or more of ethylene bis-stearamide, grafted ethylene bis-stearamide, silicone and metal soap salt. The present invention preferably adopts silicone. Silicone can not only reduce the melting pressure, melt viscosity, and internal stress of the resin composition of the present invention during the extrusion process, but also significantly increase the oxygen index content of the resin composition, and can greatly increase the Surface finish of the resin composition.
根据本发明提供的组合物，所述抗氧剂为本领域技术人员公知的各种抗氧剂，例如该抗氧剂为含有主抗氧剂和辅助抗氧剂的抗氧剂，且主抗氧剂与辅助抗氧剂的重量比为1∶1-4，所述主抗氧剂为受阻酚类抗氧剂，所述辅助抗氧剂为亚磷酸酯类抗氧剂；受阻酚类抗氧剂的例子包括抗氧剂1098和1010(Ciba公司的抗氧剂牌号)，抗氧剂1098的主要成分为N，N′-双-(3-(3，5-二叔丁基-4-羟基苯基)丙酰基)己二胺，抗氧剂1010的主要成分为四[3-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇。亚磷酸酯类抗氧剂的例子为抗氧剂168(Ciba公司的抗氧剂牌号)，它的主要成分为三(2，4-二叔丁基苯基)亚磷酸酯。本发明优选采用抗氧剂1010和抗氧剂168的混合物。According to the composition provided by the present invention, the antioxidant is various antioxidants known to those skilled in the art, for example, the antioxidant is an antioxidant containing a main antioxidant and an auxiliary antioxidant, and the main antioxidant The weight ratio of oxygen agent to auxiliary antioxidant is 1: 1-4, the main antioxidant is hindered phenolic antioxidant, and the auxiliary antioxidant is phosphite antioxidant; hindered phenolic antioxidant The example of oxygen agent comprises antioxidant 1098 and 1010 (the antioxidant trade mark of Ciba Company), and the main component of antioxidant 1098 is N, N '-bis-(3-(3,5-di-tert-butyl-4 -Hydroxyphenyl)propionyl)hexamethylenediamine, the main component of antioxidant 1010 is tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol. An example of a phosphite antioxidant is Antioxidant 168 (antioxidant brand of Ciba Company), whose main component is tris(2,4-di-tert-butylphenyl)phosphite. The present invention preferably employs a mixture of Antioxidant 1010 and Antioxidant 168.
在优选情况下，所述加工助剂还可采用协效阻燃剂，基于基于100重量份的氢化苯乙烯-丁二烯嵌段共聚物，所述协效阻燃剂的含量为1-5重量份。所选协效阻燃剂主要可以使本发明所使用的复合阻燃剂在树脂中的分散非常均匀，可以极大地发挥复合阻燃剂的阻燃性能，而基体树脂SEBS与分散均匀的复合阻燃剂之间也具有较强的结合力，可形成网状结构，因此在高温高湿的情况下工作，本发明的树脂组合物也不会出现龟裂、易撕裂、“冒霜”以及阻燃剂失效等现象。可选用的商购的协效阻燃剂为佛山维科德产的阻燃协效剂HFR-01。Preferably, the processing aid can also use a synergistic flame retardant, based on 100 parts by weight of hydrogenated styrene-butadiene block copolymer, the content of the synergistic flame retardant is 1-5 parts by weight. The selected synergistic flame retardant can mainly make the dispersion of the composite flame retardant used in the present invention very uniform in the resin, and can greatly exert the flame retardant performance of the composite flame retardant, while the matrix resin SEBS and the uniformly dispersed composite flame retardant Combustion agents also have a strong binding force and can form a network structure. Therefore, the resin composition of the present invention will not appear cracks, easy to tear, "frost" and Flame retardant failure and so on. An optional commercially available synergistic flame retardant is the flame retardant synergist HFR-01 produced by Foshan Vecode.
本发明的阻燃树脂组合物的制备方法包括将组合物的各成分按照配比混合均匀，送入双螺杆挤出机中挤出，然后冷却切粒，即可得到本发明的阻燃树脂组合物。The preparation method of the flame retardant resin composition of the present invention includes mixing the components of the composition evenly according to the proportion, feeding them into a twin-screw extruder for extrusion, and then cooling and cutting into pellets to obtain the flame retardant resin composition of the present invention. thing.
下面采用实施例的方式对本发明进行进一步详细地描述。The present invention will be further described in detail by way of examples below.
实施例1Example 1
将氢化苯乙烯-丁二烯嵌段共聚物树脂(SEBS)(巴陵石化，YH-561)100重量份，二甲基硅油(德国瓦克，AK201)30重量份，聚苯乙烯(杨子巴斯夫，476L)15重量份，复合阻燃剂40重量份，乙烯丙烯酸酯马来酸酐共聚物(阿科玛，LOTADER 4210)10重量份，防滴落剂PTFE 1重量份，硬脂酸钙1重量份，硅铜3重量份以及抗氧剂1010和抗氧剂168各1重量份在高速混合机(张家港亿利机械SHR-500A)中以高速档充分混合10分钟。其中，在复合阻燃剂中，磷酸酯、聚磷酸胺和白度包覆化红磷的重量比为1∶0.1∶2，磷酸酯为双酚A双(二苯基磷酸酯)，聚磷酸胺的聚合度为1500，包覆白度化红磷为连云港信托硅化FRW30。With 100 parts by weight of hydrogenated styrene-butadiene block copolymer resin (SEBS) (Baling Petrochemical, YH-561), 30 parts by weight of simethicone oil (Wacker, AK201), polystyrene (poplar BASF, 476L) 15 parts by weight, composite flame retardant 40 parts by weight, ethylene acrylate maleic anhydride copolymer (Arkema, LOTADER 4210) 10 parts by weight, anti-dripping agent PTFE 1 part by weight, calcium stearate 1 Parts by weight, 3 parts by weight of silicon copper and 1 part by weight of each of antioxidant 1010 and antioxidant 168 were fully mixed for 10 minutes at high speed in a high-speed mixer (Zhangjiagang Yili Machinery SHR-500A). Among them, in the composite flame retardant, the weight ratio of phosphoric acid ester, polyphosphate amine and whiteness-coated red phosphorus is 1:0.1:2, the phosphoric acid ester is bisphenol A bis(diphenyl phosphate), polyphosphoric acid The degree of polymerization of the amine is 1500, and the whiteness red phosphorus coated is Lianyungang trust siliconized FRW30.
将混合后的物料通过双螺杆挤出机(南京新时代XSD-75型)挤出，双螺杆挤出机各区温度分别设置为：The mixed material is extruded through a twin-screw extruder (Nanjing Xinshidai XSD-75 type), and the temperature of each zone of the twin-screw extruder is set as follows:
一区150-155℃ 二区155-160℃ 三区160-170℃Zone 1 150-155℃ Zone 2 155-160℃ Zone 3 160-170℃
四区170-180℃ 五区180-190℃ 六区170-180℃Zone 4 170-180℃ Zone 5 180-190℃ Zone 6 170-180℃
七区170-180℃ 八区155-165℃ 九区155-165℃Zone 7 170-180℃ Zone 8 155-165℃ Zone 9 155-165℃
在双螺杆挤出机的螺杆转速为250r/min，喂料速度为50r/min的条件下挤成条状，经冷却后切粒，得到本发明的阻燃树脂组合物。The twin-screw extruder screw speed is 250r/min, and the feeding speed is 50r/min, extruded into strips, cooled and pelletized to obtain the flame retardant resin composition of the present invention.
实施例2Example 2
按照实施例1中描述的方法制备本发明的阻燃树脂组合物，不同的是，采用氮磷复合阻燃剂(杭州捷而思，PNP1)替换复合阻燃剂。The flame retardant resin composition of the present invention was prepared according to the method described in Example 1, except that a nitrogen-phosphorus composite flame retardant (Hangzhou Jieersi, PNP1) was used to replace the composite flame retardant.
实施例3Example 3
将SEBS树脂100重量份，苯基硅油(深圳市吉鹏硅氟材料，255-A/500CS)40重量份，聚丙烯20重量份，复合阻燃剂25重量份，乙烯丙烯酸甲酯共聚物(EMA)15重量份，防滴落剂PTFE 5重量份，硬脂酸钙0.3重量份，硅铜0.3重量份以及抗氧剂1010和抗氧剂168各0.2重量份在高速混合机中以高速档充分混合10分钟。其中，在复合阻燃剂中，磷酸酯、聚磷酸胺和白度化包覆红磷的重量比为1∶2∶5，磷酸酯为间苯二酚(二苯基磷酸酯)，聚磷酸胺的聚合度为1800，白度化包覆红磷为连云港信托硅化FRW30。100 parts by weight of SEBS resin, 40 parts by weight of phenyl silicone oil (Shenzhen Jipeng silicon fluoride material, 255-A/500CS), 20 parts by weight of polypropylene, 25 parts by weight of composite flame retardant, ethylene methyl acrylate copolymer ( EMA) 15 parts by weight, 5 parts by weight of anti-dripping agent PTFE, 0.3 parts by weight of calcium stearate, 0.3 parts by weight of silicon copper and each 0.2 parts by weight of antioxidant 1010 and antioxidant 168 in a high-speed mixer with a high speed gear Mix well for 10 minutes. Among them, in the composite flame retardant, the weight ratio of phosphoric acid ester, polyphosphate amine and whitening coated red phosphorus is 1:2:5, the phosphoric acid ester is resorcinol (diphenyl phosphate), polyphosphoric acid The degree of polymerization of the amine is 1800, and the red phosphorus coated with whiteness is Lianyungang trust silicified FRW30.
将混合后的物料通过双螺杆挤出机挤出，双螺杆挤出机各区温度分别设置为：The mixed material is extruded through a twin-screw extruder, and the temperature in each zone of the twin-screw extruder is set to:
一区150-155℃ 二区155-160℃ 三区160-170℃Zone 1 150-155℃ Zone 2 155-160℃ Zone 3 160-170℃
四区170-180℃ 五区180-190℃ 六区170-180℃Zone 4 170-180℃ Zone 5 180-190℃ Zone 6 170-180℃
七区170-180℃ 八区155-165℃ 九区155-165℃Zone 7 170-180℃ Zone 8 155-165℃ Zone 9 155-165℃
在双螺杆挤出机的螺杆转速为250r/min，喂料速度为50r/min的条件下挤成条状，经冷却后切粒，得到本发明的阻燃树脂组合物。The twin-screw extruder screw speed is 250r/min, and the feeding speed is 50r/min, extruded into strips, cooled and pelletized to obtain the flame retardant resin composition of the present invention.
实施例4Example 4
将SEBS树脂100重量份，硅油(道康宁，DC 200-500)60重量份，聚丙烯30重量份，复合阻燃剂20重量份，协效阻燃剂(佛山维科德，HFR-01)5重量份，乙烯丙烯酸甲酯共聚物(EMA)5重量份，防滴落剂PTFE 1重量份，硬脂酸钙1重量份，硅铜3重量份以及抗氧剂1010和抗氧剂168各1重量份在高速混合机以高速档充分混合10分钟。其中，在复合阻燃剂中，磷酸酯、聚磷酸胺和白度化包覆红磷的重量比为1∶1∶1，磷酸酯为磷酸三苯酯，聚磷酸胺的聚合度为2000，白度化包覆红磷为连云港信托硅化FRW30。100 parts by weight of SEBS resin, 60 parts by weight of silicone oil (Dow Corning, DC 200-500), 30 parts by weight of polypropylene, 20 parts by weight of composite flame retardant, synergistic flame retardant (Foshan Vecode, HFR-01) 5 Parts by weight, 5 parts by weight of ethylene methyl acrylate copolymer (EMA), 1 part by weight of anti-dripping agent PTFE, 1 part by weight of calcium stearate, 3 parts by weight of silicon copper and each 1 part of antioxidant 1010 and antioxidant 168 Parts by weight were fully mixed for 10 minutes in a high-speed mixer with a high speed gear. Among them, in the composite flame retardant, the weight ratio of phosphoric acid ester, polyphosphate amine and whitening coated red phosphorus is 1:1:1, the phosphoric acid ester is triphenyl phosphate, and the polymerization degree of polyphosphate amine is 2000. The whiteness coated red phosphorus is Lianyungang trust silicified FRW30.
将混合后的物料通过双螺杆挤出机挤出，双螺杆挤出机各区温度分别设置为：The mixed material is extruded through a twin-screw extruder, and the temperature in each zone of the twin-screw extruder is set to:
一区150-155 ℃ 二区155-160℃ 三区160-170℃Zone 1 150-155℃ Zone 2 155-160℃ Zone 3 160-170℃
四区170-180℃ 五区180-190℃ 六区170-180℃Zone 4 170-180℃ Zone 5 180-190℃ Zone 6 170-180℃
七区170-180℃ 八区155-165℃ 九区155-165℃Zone 7 170-180°C Zone 8 155-165°C Zone 9 155-165°C
在双螺杆挤出机的螺杆转速为250r/min，喂料速度为50r/min的条件下挤成条状，经冷却后切粒，得到本发明的阻燃树脂组合物。The twin-screw extruder screw speed is 250r/min, and the feeding speed is 50r/min, extruded into strips, cooled and pelletized to obtain the flame retardant resin composition of the present invention.
对比例1Comparative example 1
按照实施例1中描述的方法制备本发明的阻燃树脂组合物，不同的是，采用白油(无锡永真工业油品有限公司，26#白油)替换硅油。The flame retardant resin composition of the present invention was prepared according to the method described in Example 1, except that white oil (Wuxi Yongzhen Industrial Oil Co., Ltd., 26# white oil) was used instead of silicone oil.
性能测试Performance Testing
采用ASTM D638的测试标准来测试断裂伸长率(％)和100％定伸强度(MPa)；The test standard of ASTM D638 is used to test the elongation at break (%) and 100% tensile strength (MPa);
采用ASTM D2240的测试标准来测试邵式硬度(A)。The Shore hardness (A) is tested using the test standard of ASTM D2240.
对实施例1-4和对比例1中所得到的组合物进行性能测试，所得到的结果列于表1中。Performance tests were performed on the compositions obtained in Examples 1-4 and Comparative Example 1, and the results obtained are listed in Table 1.
表1Table 1
从表1中可以看出，本发明的阻燃树脂组合物的断裂伸长率和100％定伸强度很高，远远大于对比例1中的阻燃树脂组合物。另外，采用氮磷复合阻燃剂作为阻燃剂的实施例2所得到的阻燃树脂组合物的力学性能尽管比对比例1中的阻燃树脂组合物好，但比本发明的实施例1、3和4中所得到的阻燃树脂组合物的都差，说明，采用本发明的复合阻燃剂可以使阻燃树脂组合物的力学性能更好。It can be seen from Table 1 that the elongation at break and 100% modulus of the flame retardant resin composition of the present invention are very high, which are far greater than those of the flame retardant resin composition in Comparative Example 1. In addition, although the mechanical properties of the flame retardant resin composition obtained in Example 2 using a nitrogen-phosphorus composite flame retardant as a flame retardant are better than those of the flame retardant resin composition in Comparative Example 1, they are better than those of Example 1 of the present invention. , 3 and 4 are all poor flame retardant resin compositions, indicating that the composite flame retardant of the present invention can make the mechanical properties of flame retardant resin compositions better.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101880460ACN101440190B (en) | 2007-11-22 | 2007-11-22 | Flame retardant resin composition |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101880460ACN101440190B (en) | 2007-11-22 | 2007-11-22 | Flame retardant resin composition |
| Publication Number | Publication Date |
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| CN101440190A CN101440190A (en) | 2009-05-27 |
| CN101440190Btrue CN101440190B (en) | 2010-12-22 |
| Application Number | Title | Priority Date | Filing Date |
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| CN2007101880460AActiveCN101440190B (en) | 2007-11-22 | 2007-11-22 | Flame retardant resin composition |
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